JP2005255843A - Solventless liquid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solventless liquid composition with high versatility, free from evaporation of organic solvents, excellent in safety, reducing environmental load. <P>SOLUTION: The invention relates to the solventless liquid composition comprising at least a kind of organic low molecular weight compound containing a reactive group (in the proviso that the compound excludes ionic liquid containing polymerizable group) and/or at least a kind of high molecular weight compound and at least a kind of ionic liquid containing polymerizable group and a reactive diluent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a solventless liquid composition, and more specifically, to a solventless liquid composition containing a polymerizable group-containing ionic liquid as a reactive diluent.

Conventionally, solvent-based adhesives and solvent-based paints have been widely used not only industrially but also at home in various fields such as packaging / binding, civil engineering / architecture, electronic and electrical equipment, automotive materials, optical components, etc. .
These adhesives and paints are generally applied as a composition in which an adhesive component or paint component is dissolved in an organic solvent or the like, applied to the adherend surface or the paint surface, and then the solvent is removed and solidified. It is used.

By the way, since these solvent-based adhesives and solvent-based paints use a large amount of organic solvent, it is necessary to pay attention to the work environment from the viewpoint of safety. Be careful.
In the construction field, the residual organic solvent may gradually evaporate even after construction, which may harm human health. This phenomenon is called sick house syndrome and is a serious problem.
Furthermore, in recent years, environmental considerations such as regulation of the release of volatile organic compounds (VOC) into the atmosphere have become necessary, and the need for deorganic solvents is increasing.

In order to eliminate the disadvantages of this organic solvent, in recent years, a solventless adhesive that does not use a volatile organic solvent (Patent Document 1: Japanese Patent Laid-Open No. 9-20878, Patent Document 2: Japanese Patent Laid-Open No. 10-71664) Patent Document 3: JP-A-11-302621, Patent Document 4: JP-A 2001-164229, Patent Document 5: JP-A 2001-172602, Patent Document 6: JP-A-2001-214144), Solventless paints (Patent Document 7: JP 2002-146284 A, Patent Document 8: JP 2002-146285 A, Patent Document 9: JP 2002-322419 A) are being developed.
These solvent-free adhesives and paints can be operated without using organic solvents such as toluene by devising the main material and lowering its viscosity. The basic performance is also demonstrated.

  However, these adhesives and paints have a problem of lack of versatility because it is necessary to improve the suitable molecular design according to the material used as the main agent and the purpose of use. In addition, since it is difficult to use a solid resin or a resin with extremely high viscosity as an essential component, there is a problem that usable materials are limited as compared with solvent-type adhesives and paints.

On the other hand, a solventless coating composition using a reactive diluent that is non-volatile at room temperature and can dissolve a resin having a functional group as a main agent has also been reported (Patent Document 10: JP-A-6-299119). Issue gazette). By using this reactive diluent, not only can the resin itself be unsuitable for coating applications because the viscosity is too high, but the reactive diluent itself can be used as a functional group of the resin. Since it reacts and contributes to coating film formation, there exists an advantage that the problem that a residual organic solvent volatilizes does not arise.
However, the reactive diluent used in Patent Document 10 is still insufficient in terms of the solubility of the main agent such as a resin or an inorganic substance.

Japanese Patent Laid-Open No. 9-20878 Japanese Patent Laid-Open No. 10-71664 Japanese Patent Application Laid-Open No. 11-302621 JP 2001-164229 A JP 2001-172602 A JP 2001-214144 A JP 2002-146284 A JP 2002-146285 A JP 2002-322419 A JP-A-6-299119

  The present invention has been made in view of such circumstances, and has a high general-purpose solvent-free liquid composition and solvent-free adhesion that are excellent in safety without volatilization of organic solvents and can reduce environmental burden. It is an object to provide an agent, a solventless paint and an antistatic agent.

  As a result of intensive studies to achieve the above object, the present inventors have used a solvent-free liquid composition containing an ionic liquid having a polymerizable group introduced as a reactive diluent as an adhesive or a paint. The ionic liquid stays in the adhesive layer or coating film due to the polymerization reaction, so it can solve various problems that have occurred with solvent-based adhesives, etc., and it has excellent safety, environmental adaptability and versatility. The present invention has been completed by finding that it can be a composition and that such a polymerizable group-containing ionic liquid is also suitable as an antistatic agent.

〔式中、Ｘは重合性官能基を示し、Ａはアルキレンオキサイド単位を含んでいてもよい炭素数１〜１５の直鎖状または分岐鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、これらＲ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。〕
３． 前記重合性基含有イオン性液体が、下記一般式（２）で示されることを特徴とする２の無溶剤型液状組成物、

〔式中、Ｘは重合性官能基を示し、Ｂはエチレンオキサイド単位を含んでいてもよい炭素数１〜４の直鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、Ｒ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。Ｙは一価のアニオンを示す。〕
４． 接着剤用または塗料用であることを特徴とする１〜３のいずれかの無溶剤型液状組成物、
５． 重合性基含有イオン性液体からなることを特徴とする反応性希釈剤、
６． 前記重合性基含有イオン性液体が、下記一般式（１）、（３）および（４）から選ばれる少なくとも１種であることを特徴とする５の反応性希釈剤、

〔式中、Ｘは重合性官能基を示し、Ａはアルキレンオキサイド単位を含んでいてもよい炭素数１〜１５の直鎖状または分岐鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、これらＲ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。Ｒ⁴は炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示す。Ｙは一価のアニオンを示す。〕
７． 前記重合性基含有イオン性液体が、下記一般式（２）で示されることを特徴とする５の反応性希釈剤、

〔式中、Ｘは重合性官能基を示し、Ｂはエチレンオキサイド単位を含んでいてもよい炭素数１〜４の直鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、Ｒ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。Ｙは一価のアニオンを示す。〕
８． ５〜７のいずれかの反応性希釈剤を用いてなることを特徴とする無溶剤型接着剤、
９． ５〜７のいずれかの反応性希釈剤を用いてなることを特徴とする無溶剤型塗料、
１０． 重合性基含有イオン性液体からなることを特徴とする帯電防止剤、
１１． 前記重合性基含有イオン性液体が、下記一般式（１）、（３）および（４）で示される４級アンモニウム塩型イオン性液体から選ばれる少なくとも１種である１０の帯電防止剤、

〔式中、Ｘは重合性官能基を示し、Ａはアルキレンオキサイド単位を含んでいてもよい炭素数１〜１５の直鎖状または分岐鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、これらＲ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。Ｒ⁴は炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示す。Ｙは一価のアニオンを示す。〕
１２． 前記重合性基含有イオン性液体が、下記一般式（２）で示されることを特徴とする１０の帯電防止剤

〔式中、Ｘは重合性官能基を示し、Ｂはエチレンオキサイド単位を含んでいてもよい炭素数１〜４の直鎖状炭化水素基を示し、Ｒ¹〜Ｒ³は互いに同一または異種の炭素数１〜１０のアルキル基、アルコキシ基、アリール基または重合性基含有アルキル基を示し、Ｒ¹〜Ｒ³のいずれか２個の基が環を形成していてもよい。Ｙは一価のアニオンを示す。〕
を提供する。 That is, the present invention
1. At least one reactive group-containing low molecular weight organic compound (excluding the polymerizable group-containing ionic liquid) and / or at least one polymer compound and at least one polymerizable group-containing ionic liquid A solvent-free liquid composition comprising a reactive diluent,
2. The solvent-free liquid composition according to 1, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (1):

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . ]
3. The solvent-free liquid composition according to 2, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2):

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]
4). One of the solvent-free liquid compositions according to 1 to 3, which is for adhesives or paints,
5). A reactive diluent comprising a polymerizable group-containing ionic liquid,
6). The reactive diluent according to 5, wherein the polymerizable group-containing ionic liquid is at least one selected from the following general formulas (1), (3) and (4):

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group. Y represents a monovalent anion. ]
7). The reactive diluent according to 5, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2):

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]
8). A solventless adhesive, characterized by using any of the reactive diluents of 5-7,
9. A solventless paint characterized by using any of the reactive diluents of 5-7,
10. An antistatic agent comprising a polymerizable group-containing ionic liquid,
11. 10 antistatic agents, wherein the polymerizable group-containing ionic liquid is at least one selected from quaternary ammonium salt type ionic liquids represented by the following general formulas (1), (3) and (4):

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group. Y represents a monovalent anion. ]
12 The antistatic agent according to 10, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2):

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]
I will provide a.

According to the solvent-free liquid composition of the present invention, at least one reactive group-containing low molecular organic compound (except for the polymerizable group-containing ionic liquid) and / or at least one polymer compound, Since it contains a reactive diluent comprising at least one polymerizable group-containing ionic liquid, it is excellent in safety and environmental adaptability. In other words, not only does it contain volatile solvents that are commonly used in solvent-based paints and adhesives, but when this solventless liquid composition is used as an adhesive or paint, Since the liquid remains in the adhesive layer or the coating film due to the polymerization reaction, adverse effects on the human body and the environment due to solvent volatilization can be prevented as much as possible.
In addition, the reactive diluent comprising a polymerizable group-containing ionic liquid is not only compatible with many organic compounds, but also can dissolve inorganic compounds that are insoluble or difficult to dissolve in organic solvents. Various functions can be imparted to the composition.

Since the polymerizable group-containing ionic liquid used as the reactive diluent is changed into an adhesive or a coating film component by the polymerization reaction, a drying step for removing the solvent is not required after the polymerization. For this reason, the work process of the whole adhesion | attachment and coating can be simplified, and improvement of productivity etc. can be aimed at.
Furthermore, the polymerizable group-containing ionic liquid used in the solventless liquid composition of the present invention is a compound having a cation and an anion in the molecule, and functions also as an antistatic agent. Therefore, the object to be coated, the object to be adhered, and the like have the same antistatic property although the degree varies depending on the content of the polymerizable group-containing ionic liquid. When the polymerizable group-containing ionic liquid is used as a reactive diluent as in the present invention, the adhesive layer or the coating film is used as compared with the case where a quaternary ammonium salt type compound having no polymerizable group is used as an antistatic agent. Since the proportion of electric charges present therein can be increased, excellent antistatic properties are imparted. In addition, the antistatic agent remains in the adhesive layer or the like by the polymerization reaction, and does not cause problems such as bleed out.

Hereinafter, the present invention will be described in more detail.
The solventless liquid composition according to the present invention comprises at least one reactive group-containing low molecular weight organic compound (excluding a polymerizable group-containing ionic liquid) and / or at least one polymer compound, And a reactive diluent composed of one kind of polymerizable group-containing ionic liquid.
The polymerizable group-containing ionic liquid used as the reactive diluent is not particularly limited as long as it is an ionic liquid into which a polymerizable group has been introduced, but the above general formulas (1), (3) and It is preferably at least one selected from quaternary salt type ionic liquids represented by (4). Among these, considering the production cost, the polymerizable group-containing ionic liquid represented by the above general formula (1), particularly the polymerizable group-containing ionicity represented by the formula (2), which is inexpensive and relatively easy to synthesize. It is preferable to use a liquid.
In addition, a plurality of polymerizable group-containing ionic liquids can be used in combination, and in this way, it is easy to adjust the viscosity of the adhesive and the coating film component to suit the purpose of use, and adhesion It is possible to modify the toughness of layers and coatings.

  In the above formulas, the polymerizable functional group X is not particularly limited as long as it is a group that can participate in the polymerization reaction. For example, α, β-unsaturated carbonyl group such as (meth) acryl group, α, β-unsaturated nitrile group, conjugated diene, carboxylic acid vinyl ester group having reactive unsaturated bond, carboxyl group, carbonyl group , Epoxy group, isocyanate group, hydroxy group, amide group, cyano group, amino group, chloromethyl group, glycidyl ether group, lithio group, ester group, formyl group, nitrile group, nitro group, carbodiimide group, oxazoline group, etc. However, since the raw material is inexpensive and generally exhibits a property of excellent weather resistance and high transparency after polymerization, an α, β-unsaturated carbonyl group such as a (meth) acryl group is particularly used. Is preferred.

Examples of the linear or branched divalent hydrocarbon group A having 1 to 15 carbon atoms which may contain an alkylene oxide unit include divalent hydrocarbon groups such as methylene, ethylene, propylene, butylene and pentylene, And groups formed by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to these groups.
Examples of the straight-chain hydrocarbon group B having 1 to 4 carbon atoms that may contain an ethylene oxide unit include methylene, ethylene, propylene, butylene groups, and groups formed by adding ethylene oxide to these groups. Can be mentioned.
In addition, it is preferable that the addition mole number of alkylene (ethylene) oxide is 1-7.
Examples of the alkyl group having 1 to 10 carbon atoms of R ^{1 to} R ⁴ , an alkoxy group, an aryl group, and a polymerizable group-containing alkyl group include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, Examples include methoxy, ethoxy, propoxy, isopropoxy, s-butoxy, t-butoxy group, phenyl group, benzyl group, and groups in which the hydrogen atom of these groups is substituted with the above-described polymerizable group. In addition, the compound in which any two groups of R ^{1 to} R ³ form a ring is a polymerization having an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring or the like in the formulas (1) and (2). An ionic liquid containing a functional group.

The monovalent anion Y is not particularly limited as long as a polymerizable group-containing ionic liquid can be formed. Halogen anion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , AlCl ₄ ⁻ , HSO ₄ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₄ ⁻ , CH ₃ SO ₄ ⁻ , CF ₃ CO ₂ ⁻ , CH ₃ CO ₂ ⁻ , CF ₃ C ₆ F ₄ SO ₃ ⁻ , CF ₃ C ₆ H ₄ SO ₃ ⁻ , CH ₃ C ₆ H ₄ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) (CF ₃ At least one anion selected from SO ₂ ) N ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and the like can be used.
Among these, (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) (CF ₃ SO ₂ ) N ⁻ , ( CF ₃ SO ₂ ) ₂ N ⁻ is preferable, and (CF ₃ SO ₂ ) ₂ N ⁻ is particularly preferable in consideration of availability and manufacturing cost.

  Specific examples of the polymerizable group-containing ionic liquid include compounds represented by the following formulae. These compounds can be obtained, for example, by reacting an alkyl tertiary amine having a polymerizable group with an alkyl halide or the like to form a quaternization and then performing an exchange reaction with a desired anion. It is also possible to introduce a desired anion simultaneously with quaternization, for example, by reacting tertiary amine with methyl paratosylate.

  Moreover, the compound shown by a following formula can also be mentioned as a specific example of a polymeric group containing ionic liquid. These compounds can be exchanged with a desired anion after reacting (meth) acryloyl chloride with an imidazolium salt or pyridinium salt obtained by reacting N-alkylimidazole or pyridine with 2-chloroethanol or the like, for example. Can be obtained. It can also be obtained by reacting N-alkylimidazole or pyridine with 2-((meth) acryloylethyl) chloride and then performing an exchange reaction with a desired anion.

  The content of the polymerizable group-containing ionic liquid in the solvent-free liquid composition of the present invention is not particularly limited, but the solvent-free liquid composition has an appropriate viscosity, such as coating. In order to facilitate the work, the content is preferably 30 to 90% by mass, and more preferably 50 to 80% by mass.

The present invention is characterized in that a polymerizable group-containing ionic liquid is used as a reactive diluent for a solvent-free liquid composition, and the reactive group-containing low molecule contained in the solvent-free liquid composition. The organic compound and the polymer compound are not particularly limited. Specific examples of these compounds include various compounds widely used as a main agent, a curing agent and the like in the adhesive and paint field.
Examples of reactive group-containing low molecular weight organic compounds include α, β-unsaturated carbonyl groups, α, β-unsaturated nitrile groups, conjugated dienes, carboxylic acid vinyl ester groups, carboxyl groups, carbonyl groups, epoxy groups, and isocyanate groups. Group, hydroxy group, amide group, cyano group, amino group, chloromethyl group, glycidyl ether group, ester group, formyl group, nitrile group, nitro group, carbodiimide group, oxazoline group, carbon-carbon double bond-containing group, carbon A compound having at least one group selected from a carbon triple bond-containing group and the like can be used.

  Specific examples of the low molecular organic compound include (meth) acrylic acid-based low molecules such as (meth) acrylic acid, (meth) acrylic acid-2-ethylhexyl, 2-hydroxyethyl acrylate, methyl (meth) acrylate, and the like. Compounds, nitrile low molecular weight compounds such as acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile, amide low molecular weight compounds such as (meth) acrylamide, N-methyl (meth) acrylamide, methylol acrylamide, toluene diisocyanate, hexa Isocyanate-based low molecular compounds such as methylene diisocyanate, carbon-carbon double bond-containing low molecular compounds such as styrene, butadiene, vinyl chloride and vinyl acetate, and carbon-carbon such as 1-butyn-1-ol and 1,6-heptadiyne Low triple bond content Child compounds.

As the polymer compound, for example, at least one selected from a fluororesin, an acrylic resin, a polyester resin, an epoxy resin, a melamine resin, a silicone resin, a polyurethane resin, and the like can be used.
Examples of the fluororesin include, for example, a binary copolymer of a fluorine-containing vinyl monomer and a functional group-containing vinyl monomer, a terpolymer of a fluorine-containing vinyl monomer, a functional group-containing vinyl monomer, and other copolymerizable vinyl monomers. Etc.
Examples of the fluorine-containing vinyl monomer include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per) fluoroalkyltrifluoro. Examples include vinyl ether.

  Examples of the functional group-containing vinyl monomer include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, and hydroxybutyl vinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, and diethylene glycol mono (meth) acrylate. Hydroxyl group-containing vinyl monomers such as hydroxyalkyl (meth) acrylate; carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid; dimethylaminoethyl vinyl ether, dimethylamino Propyl vinyl ether, N, N-dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate Include amino group-containing vinyl monomers of.

Examples of other copolymerizable vinyl monomers include alkyl vinyl ethers, aliphatic carboxylic acid vinyl esters, aromatic carboxylic acid vinyl esters, epoxy group-containing vinyl monomers, carboxyl group-containing vinyl monomers, halogenated vinyl monomers, and aromatic vinyls. Monomers, (meth) acrylic acid derivatives and the like.
Each of the above-mentioned fluorine-containing vinyl monomer, functional group-containing vinyl monomer, and copolymerizable vinyl monomer can be used singly or in combination of two or more.

Examples of the acrylic resin include a polymer obtained by polymerization and copolymerization of acrylic and methacrylic monomers, and a polymer obtained by copolymerization of acrylic and methacrylic monomers and monomers copolymerizable therewith. Is mentioned.
Examples of acrylic and methacrylic monomers include acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth) acrylate. , T-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , (Meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide, etc. (Meth) acrylamides and the like. Also, methoxydiethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, NK ester 2G (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK ester 9G (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK ester 23G (Shin-Nakamura) (Meth) acrylic acid monoesters or (meth) acrylic acid diesters having an alkylene oxide as a repeating unit, such as NK ester TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) ) A polyfunctional (meth) acrylic acid derivative having a plurality of acrylic groups in the molecule can be used.
The copolymerizable monomer may be any monomer having a functional group copolymerizable with an acrylic or methacrylic monomer, and is not particularly limited. For example, (meth) acrylonitrile , Vinyl chloride, vinylidene chloride, vinyl acetate, dimethyl itaconate, diethyl maleate, ethyl vinyl ether, styrene, vinyl toluene, α-methyl styrene, vinyl pyridine, divinyl benzene, divinyl adipate, and the like.

  Examples of polyester resins include polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, trimellitic acid, ethylene glycol, diethylene glycol, propylene Glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, hydroquinone bis (hydroxyethyl ether), 2,2 , 4-trimethyl-1,3-pentanediol, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, tris (hydroxyethyl) isocyanurate DOO, cyclohexanediol, cyclohexanedimethanol, include resins obtained by condensation under conditions of a polyol by conventional methods hydroxyl excess, such as xylylene glycol.

Examples of the melamine resin include a resin obtained by reacting melamine with formalin and modifying an initial condensate of methylolated melamine with butanol or the like, and a resin that is soluble in an organic solvent is preferable.
Examples of the epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, other polyphenol types, polyglycidylamine type, alcohol type, and ester type.

The silicone resin is, for example, a resin based on a polysiloxane obtained by polycondensation of silanol by hydrolysis of dimethyldichlorosilane, methylphenyldichlorosilane, etc., and a part of dimethylsiloxane or methylphenylsiloxane unit is a vinyl group. And vinyl silicone-based and phenyl vinyl silicone-based silicone resins substituted.
Examples of the polyurethane resin include isocyanates such as 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, and hexamethylene diisocyanate, and glycols such as ethylene oxide, propylene oxide, propylene glycol, and 1,4-butanediol. Examples thereof include polyurethane resins obtained by addition reaction of one or more kinds.

The above-described polymer compound may or may not have a reactive group, but in the solventless liquid composition of the present invention, a polymerizable group-containing ionic liquid used as a reactive diluent. Considering that it is necessary to finally polymerize, it is preferable to use a polymer compound containing a reactive group.
Specific examples include a fluororesin, an acrylic resin, a polyester resin, an epoxy resin, a melamine resin, a silicone resin, and a polyurethane resin containing a reactive group.

As described above, the solventless liquid composition of the present invention comprises various reactive group-containing low molecular organic compounds and / or polymer compounds and a reactive diluent comprising a polymerizable group-containing ionic liquid. The ratio of the reactive group-containing low molecular organic compound and / or polymer compound to the polymerizable group-containing ionic liquid in the composition is, for example, 70:30 in terms of mass ratio. To 1:99, preferably 60:40 to 10:90, more preferably 50:50 to 20:80.
In addition, the solvent-free liquid composition of the present invention includes optional components used for adhesives, paints, and the like as required, in addition to the reactive group-containing low molecular weight organic compound, polymer compound, and reactive diluent. It may be included.
Specific optional components include antifoaming agents, antioxidants, ultraviolet absorbers, plasticizers, surfactants, dyes, pigments, organic or inorganic fine particles, and the like.

The solvent-free liquid composition of the present invention can be prepared by any method, including a reactive group-containing low molecular organic compound and / or polymer compound, a reactive diluent comprising a polymerizable group-containing ionic liquid, and other optional components. Can be prepared by mixing them in an appropriate order and stirring them.
The liquid state is a concept including various forms such as a uniform solution, an emulsion, and a suspension.

The solventless liquid composition of the present invention is suitable as an adhesive composition and a coating composition.
The adhesive is not particularly limited, and examples thereof include epoxy resin adhesives such as epoxy-phenolic, epoxy-polyamide, epoxy-nitrile rubber, and epoxy-vulcanized acrylic rubber, and nitrile-phenolic. , Vinyl-phenolic phenol resin adhesives, acrylic resin adhesives, urethane resin adhesives, silicone adhesives, rubber adhesives, etc., and reactions contained in solventless liquid compositions The composition for adhesives required can be prepared by selecting suitably a low molecular weight organic compound and high molecular compound containing a functional group.
The solventless liquid composition of the present invention can be used for functional adhesives such as ultraviolet curable adhesives, visible curable adhesives, elastic adhesives, heat resistant adhesives, pressure sensitive adhesives, and conductive adhesives. Can also be applied.

  On the other hand, the coating material is not particularly limited. For example, nitrocellulose, alkyd resin, aminoalkyd resin, vinyl resin, acrylic resin, epoxy resin, urethane resin, polyester resin, chloride Examples include rubber-based, paint-silicone resin-based, and fluorine-resin-based paints. In this case as well, it is necessary to appropriately select the reactive group-containing low molecular weight organic compound and polymer compound contained in the solventless liquid composition. A coating composition can be prepared.

When the solventless liquid composition of the present invention is used as an adhesive composition, for example, the solventless liquid composition prepared by an appropriate technique as described above is applied to the adhesive surface of one adherend. Then, after the other adherend is laminated, fixed, etc., the reaction is performed by an appropriate method such as heating, ultraviolet irradiation, electron beam irradiation, etc., depending on the type of reactive group in the solventless liquid composition. It can be cured and bonded.
When used as a coating composition, for example, after applying a solvent-free liquid composition to the surface to be coated by an appropriate technique, the kind of reactive group in the composition is the same as in the adhesive composition. The coating film may be formed by reaction curing with a curing method according to the method.

Since the polymerizable group-containing ionic liquid in the present invention has a cation and an anion in the molecule, it can be suitably used as an antistatic agent.
Regardless of solvent type or solventless type, it can be used as an antistatic agent by adding it to a liquid composition, adding it to a composition for obtaining a resin molded product, or using it in a resin. It can be kneaded into. In this case, the blending amount of the antistatic agent in each composition is not particularly limited, and may be about 0.01 to 30% by mass in the composition.

In addition, the antistatic agent comprising the polymerizable group-containing ionic liquid is polymerized alone to produce an antistatic film (sheet), or the antistatic agent comprising the polymerizable group-containing ionic liquid is used as a resin molded product, etc. It is also possible to form an antistatic film by polymerizing it alone after being applied to the object to be coated. As the polymerization conditions, an appropriate method according to the polymerizable group such as heating, ultraviolet irradiation, electron beam irradiation, etc. may be used as described above.
Also in this case, since the polymerizable group-containing ionic liquid remains inside the film or coating due to the polymerization reaction, not only can the adverse effects on the human body and the environment due to solvent volatilization be prevented as much as possible, but also after polymerization. It does not require a drying step for solvent removal.

  When the polymerizable group-containing ionic liquid is used as an antistatic agent, only the polymerizable group-containing ionic liquid may be used, but the anti-foaming agent and the antioxidant are included in the polymerizable group-containing ionic liquid. Further, optional components such as ultraviolet absorbers, plasticizers, surfactants, dyes, pigments, organic or inorganic fine particles can be added.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

[Synthesis Example 1] Synthesis of polymerizable group-containing ionic liquid (6) 11.7 g of N, N-diethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 250 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Then, the mixture was stirred with a stirrer while cooling with ice, and 4.71 ml of iodomethane (manufactured by Sigma-Aldrich Japan Co., Ltd.) was slowly added little by little. After 30 minutes, the ice bath was removed and the mixture was stirred overnight at room temperature. The solvent was distilled off from this reaction solution under reduced pressure, and the resulting solid was recrystallized with ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)-Tetrahydrofuran system, and N, N-diethyl-N-methyl-N- (2 -Methacryloylethyl) ammonium iodine salt 18.17g was obtained.
Subsequently, 18.17 g of N, N-diethyl-N-methyl-N- (2-methacryloylethyl) ammonium iodine salt was dissolved in 50 ml of acetonitrile (manufactured by Kanto Chemical Co., Inc.). To this, 15.93 g of lithium bis (trifluoromethanesulfonic acid) imide salt (manufactured by Kanto Chemical Co., Inc.) was added, and after this completely dissolved, the mixture was further stirred for 30 minutes. Thereafter, acetonitrile was distilled off under reduced pressure, and an appropriate amount of ion-exchanged water was added to the residue for washing to remove impurities in the organic layer. Water was removed from the washed organic layer using a vacuum pump to obtain 20.71 g of a polymerizable group-containing ionic liquid (6).

[Synthesis Example 2] Synthesis of polymerizable group-containing ionic liquid (9) N- (2-acryloylethyl) -N, N, N-trimethylammonium chloride prepared in 79% by mass aqueous solution (manufactured by Kojin Co., Ltd.) ) 10.0 g was dissolved in 50 ml of ion exchange water. To this, 11.72 g of lithium bis (trifluoromethanesulfonic acid) imide salt (manufactured by Kanto Chemical Co., Inc.) was added and stirred for 60 minutes, and then the separated organic layer was separated.
An appropriate amount of ion-exchanged water was added to the separated organic layer for washing, and impurities in the organic layer were removed. Water was removed from the washed organic layer with a vacuum pump to obtain 16.27 g of a polymerizable group-containing ionic liquid (9).

[Synthesis Example 3] Synthesis of polymerizable group-containing ionic liquid (10) 7.15 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin Co., Ltd.) in 50 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was dissolved and stirred with a stirrer while cooling with ice, and 7.80 g of iodoethane (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added thereto little by little. After 30 minutes, the ice bath was removed and the mixture was stirred overnight at room temperature. The solvent of this reaction solution was distilled off under reduced pressure, and the resulting solid was recrystallized with an ethanol-tetrahydrofuran system to give 12.23 g of N- (2-acryloylethyl) N-ethyl-N, N-dimethylammonium iodine salt. Obtained.
Subsequently, 12.23 g of N- (2-acryloylethyl) -N-ethyl-N, N-dimethylammonium iodine salt was dissolved in 50 ml of ion-exchanged water. To this, 11.74 g of lithium bis (trifluoromethanesulfonic acid) imide salt was added and stirred for 60 minutes, and then the separated organic layer was separated.
An appropriate amount of ion-exchanged water was added to the separated organic layer for washing, and impurities in the organic layer were removed. Water was removed from the washed organic layer with a vacuum pump to obtain 13.28 g of a polymerizable group-containing ionic liquid (10).

[Synthesis Example 4] Synthesis of polymerizable group-containing ionic liquid (11) 10.0 g of N- (2-acryloylethyl) -N, N-dimethyl-N-phenylammonium chloride salt prepared in a 75% by mass aqueous solution was ionized. Dissolved in 50 ml of exchange water. To this, 11.24 g of lithium bis (trifluoromethanesulfonic acid) imide salt was added and stirred for 60 minutes, and then the organic layer of the separated two layers was separated.
An appropriate amount of ion-exchanged water was added to the separated organic layer for washing, and impurities in the organic layer were removed. Water was removed from the washed organic layer with a vacuum pump to obtain 13.28 g of a polymerizable group-containing ionic liquid (11).

[Synthesis Example 5] Synthesis of polymerizable group-containing ionic liquid (12) 27 g of 2- (N-methylamino) ethanol (manufactured by Kanto Chemical Co., Ltd.) and 25 g of methoxyethyl bromide (manac Co., Ltd.) were added to an autoclave. The reaction solution is filtered and distilled under reduced pressure, the fraction is separated on a silica gel column, and 2- [N-methyl-N- (2-methoxyethyl) amino] ethanol is added to 12. 05 g was obtained.
Subsequently, 12.05 g of 2- [N-methyl-N- (2-methoxyethyl) amino] ethanol was dissolved in 100 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred with a stirrer while cooling with ice. Then, 9.62 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 9.93 g of methacryloyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were gradually added and stirred overnight at room temperature. This reaction solution was extracted with tetrahydrofuran, dried over potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), filtered, and the filtrate was separated on a silica gel column to obtain N-methyl-N- (2-methoxyethyl). 5.14 g of aminoethyl methacrylate was obtained.
Subsequently, 75 ml of tetrahydrofuran was added to 5.14 g of N-methyl-N- (2-methoxyethyl) aminoethyl methacrylate, stirred with a stirrer, and 4.35 g of iodomethane (manufactured by Sigma-Aldrich Japan) was slowly added. This was stirred overnight at room temperature. The solvent of this reaction solution was distilled off under reduced pressure, and the solid content obtained was recrystallized with an ethanol: tetrahydrofuran: hexane system, and N, N-dimethyl-N- (2-methoxyethyl) -N- (methacryloylethyl) ammonium. 6.84 g of iodine salt was obtained.
Subsequently, 6.84 g of N, N-dimethyl-N- (2-methoxyethyl) -N- (methacryloylethyl) ammonium iodine salt was dissolved in 50 ml of ion-exchanged water, and stirred with a stirrer, lithium bis (trifluoro) Lomethanesulfonic acid) imide salt (manufactured by Kanto Chemical Co., Inc.) (5.72 g) was added and stirred at room temperature overnight, and the separated organic layer was separated.
An appropriate amount of ion-exchanged water was added to the separated organic layer for washing, and impurities in the organic layer were removed. Water was removed from the washed organic layer with a vacuum pump to obtain 5.20 g of a polymerizable group-containing ionic liquid (12).

[1] Adhesive composition [Examples 1 to 11]
Polymerizable group-containing ionic liquid (6) prepared in Synthesis Example 1 (Examples 1, 2, 6), Polymerizable group-containing ionic liquid (9) prepared in Synthesis Example 2 (Examples 3-6), Polymerizable group-containing ionic liquid (10) prepared in Synthesis Example 3 (Examples 7 and 8), Polymerizable group-containing ionic liquid (11) prepared in Synthesis Example 4 (Examples 9 and 10), and Synthesis Example Polymerizable group-containing ionic liquid (12) prepared in 4 (Example 11), 2-hydroxyethyl methacrylate (Mitsubishi Gas Chemical Co., Ltd., referred to as 2-HEMA), trimethylolpropane trimethacrylate (Shin Nakamura Chemical ( 2,2'-dimethoxyphenylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) which is a photopolymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. is mixed at a ratio shown in Table 1, and is a liquid composition for ultraviolet curable adhesive. Was prepared. In Example 6, the polymerizable group-containing ionic liquid (6) and the polymerizable group-containing ionic liquid (9) were mixed and used at the ratio shown in Table 1.

About the composition for adhesive agents obtained in each said Example, adhesiveness was evaluated with the following method. The results are shown in Table 2.
<Adhesion evaluation>
The adhesive composition obtained in Examples 1 to 11 was applied onto a polyethylene terephthalate film having a size of 3.0 cm × 4.0 cm in an amount of 5.0 × 10 ⁻³ g / cm ² . After another polyethylene terephthalate film of the same size was laminated from above, it was cured by irradiation with ultraviolet rays (160 W / cm ² ) for 10 seconds, and both films were adhered.
The two adhered films were peeled off, and the adhesion was evaluated according to the following criteria.
○: The film was damaged

[2] Coating composition [Example 12]
Polymerizable group-containing ionic liquid (6) 80 parts by mass, 2-hydroxyethyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.) 20 parts by mass, Macrolex Blue 3R Gran (Bayer Chemicals Co., Ltd.) 2 parts by mass, photopolymerization 0.5 parts by mass of 2,2′-dimethoxyphenylacetone as an initiator was mixed to prepare a liquid ultraviolet curable coating composition. The obtained coating composition was applied onto a 100 μm thick polyethylene-terephthalate film washed with a solvent to a thickness of 5.0 μm with a bar coater, and cured by irradiation with ultraviolet rays (160 W / cm ² ) for 10 seconds. A coating film was formed.

[Example 13]
An ultraviolet curable coating composition was prepared in the same manner as in Example 12 except that the polymerizable group-containing ionic liquid (9) was used. About the obtained coating composition, a coating film was formed in the same manner as in Example 12.

[Example 14]
Polymeric group-containing ionic liquid (9) 100 parts by mass, Macrolex Blue 3R Gran 1 part by mass, and 2,2′-dimethoxyphenylacetone 0.5 part by mass as a photopolymerization initiator are mixed to form a liquid UV-curable paint A composition was prepared. About the obtained coating composition, a coating film was formed in the same manner as in Example 12.
About the coating film formed in the said Examples 12-14, pencil hardness, adhesiveness, and surface resistance were measured and evaluated by the following method. The results are shown in Table 3.

<Evaluation of physical properties of coating film>
[1] Pencil hardness test It measured by the method based on JIS-K5600.
[2] Adhesion Test According to JIS-K5600, 1 mm square cuts were made in the vertical and horizontal directions to create 36 grids, and a grid peel test was performed with an adhesive tape to evaluate the adhesion. In Table 4, the number that was not peeled off among the 36 grids was displayed on the denominator side, and the number that was peeled off was displayed on the numerator side.
[3] Surface resistance It measured by the method based on JIS-K6911.

[Example 15]
A polymerizable group-containing ionic liquid (9) was applied to a solvent-washed 100 μm thick polyethylene-terephthalate film to a thickness of 5.0 μm with a bar coater and irradiated with ultraviolet rays (160 W / cm ² ) for 15 minutes. And cured.
When the pencil hardness, adhesion, and surface resistance of the obtained coating film were measured in the same manner as in Example 12, the pencil hardness was 4H, the adhesion was 0/36, and the surface resistance was 3.2 × 10 ⁹ (Ω).

Claims (12)

  At least one reactive group-containing low molecular weight organic compound (excluding the polymerizable group-containing ionic liquid) and / or at least one polymer compound and at least one polymerizable group-containing ionic liquid A solvent-free liquid composition comprising a reactive diluent. The solvent-free liquid composition according to claim 1, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (1).

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . ] The solvent-free liquid composition according to claim 2, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2).

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]   The solventless liquid composition according to any one of claims 1 to 3, wherein the composition is used for an adhesive or a paint.   A reactive diluent comprising a polymerizable group-containing ionic liquid. 6. The reactive diluent according to claim 5, wherein the polymerizable group-containing ionic liquid is at least one selected from the following general formulas (1), (3), and (4).

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group. Y represents a monovalent anion. ] The reactive diluent according to claim 5, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2).

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]   A solventless adhesive comprising the reactive diluent according to any one of claims 5 to 7.   A solventless paint comprising the reactive diluent according to any one of claims 5 to 7.   An antistatic agent comprising a polymerizable group-containing ionic liquid. The antistatic material according to claim 10, wherein the polymerizable group-containing ionic liquid is at least one selected from quaternary ammonium salt type ionic liquids represented by the following general formulas (1), (3) and (4). Agent.

[Wherein, X represents a polymerizable functional group, A represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms which may contain an alkylene oxide unit, and R ^{1 to} R ³ are The same or different alkyl group having 1 to 10 carbon atoms, alkoxy group, aryl group or polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. . R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group. Y represents a monovalent anion. ] The antistatic agent according to claim 10, wherein the polymerizable group-containing ionic liquid is represented by the following general formula (2).

[In the formula, X represents a polymerizable functional group, B represents a linear hydrocarbon group having 1 to 4 carbon atoms which may contain an ethylene oxide unit, and R ^{1 to} R ³ are the same or different from each other. An alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, or a polymerizable group-containing alkyl group is shown, and any two groups of R ^{1 to} R ³ may form a ring. Y represents a monovalent anion. ]